Summary
Oxidation of the (E) and (Z) isomers of 2-arylidene-1-indanones (1) and 2-arylidene-1-benzosuberones (4) by alkaline hydrogen peroxide (methodi) afforded the spiroepoxidestrans-2a–g andtrans-5a–g from both isomers as sole products in high yields. On the other hand, dimethyldioxirane epoxidation(methodii) of the (E) isomers1a–g and4a–g gave the correspondingtrans spiroepoxides in good yields, whereas the (Z) isomers1a,c,e and4a,c,e led to thecis spiroepoxides in moderate yields. Dimethyldioxirane oxidation (methodii) of (Z)-1c and (Z)-4c,e gave diones3c and6c,e as by-products as well. Epoxidation of (Z)-1a,c,e and (Z)-4a,c,e bym-chloroperoxybenzoic acid (methodiii) resulted inca. 6:1 mixtures ofcis-2a,c,e andtrans-2a,c,e orcis-5a,c,e andtrans-5a,c,e spiroepoxides.
Zusammenfassung
Oxidation der (E)- und (Z)-Isomeren von 2-Aryliden-1-indanonen (1) und 2-Aryliden-1-benzosuberonen (4) mit alkalischem Wasserstoffperoxyd (Methodei) liefert aus beiden Isomeren die Spiroepoxidetrans-2a–g undtrans-5a–g als einzige Produkte. Epoxidierung der (E)-Isomeren1a–g und4a–g mit Dimethyldioxiran (Methodeii) ergab die entsprechendentrans-Spiroepoxide in sehr guten Ausbeuten, während die (Z)-Isomeren1a,c,e und4a,c,e diecis-Spiroepoxide in nur mäßiger Ausbeute liefern. Oxidation von (Z)-1c und (Z)-4c,e mit Dimethyldioxiran (Methodeii) ergab die Dione3c und6c,e sowie einige Nebenprodukte. Wurden (Z)-1a,c,e und (Z)-4a,c,e einer Epoxidation mitm-Chlorperbenzoesäure (Methodeiii) unterworfen, entstanden 6:1-Gemische der Spiroepoxidecis-2a,c,e undtrans-2a,c,e odercis-5a,c,e undtrans-5a,c,e.
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Dedicated to Prof.W. Fleischhacker on the occasion of his 65th birthday
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Adam, W., Halász, J., Jámbor, Z. et al. Stereoselective epoxidation of 2-arylidene-1-indanones and 2-arylidene-1-benzosuberones. Monatsh Chem 127, 683–690 (1996). https://doi.org/10.1007/BF00817259
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DOI: https://doi.org/10.1007/BF00817259